FUNGICIDAL COMPOSITION COMPRISING COPPER 8-OXYQUINOLATE AND COPPER alpha -AMINO- gamma -ETHYL-THIOBUTYRATE

ABSTRACT

The present invention relates to fungicidal compositions for agricultural and horticultural use comprising one or more kinds of metal salts of Alpha -amino- gamma -ethylthio butyric acid such as copper Alpha -amino- gamma -ethylthio butyrate, or manganese Alpha -amino- gamma -ethylthio butyrate and one or more kinds of 8-oxyquinoline metal complex, such as copper or zinc 8-oxyquinolate along with adjuvants such as dispersing agent, emulsifier, or wetting agent. The composition of the present invention is remarkably effective when applied at low concentration for black spot of pear (Alernaria kikuchiana) or Helminthosporium leaf spot (Cochliobolus miyabeanus).

United States Patent 1 Ohmori et al.

FUNGICIDAL COMPOSITION COMPRISING COPPER 8- OXYQUINOLATE AND COPPER a- AMINO-y-ETHYL-THIOBUTYRATE Assignee: Nippon Kayaku Kabushiki Kaisha,

Tokyo, Japan Filed: June 6, 1969 Appl. No.: 831,252

Foreign Application Priority Data June 21, 1968 Japan ..43/42509 US. Cl. ..424/245, 424/294, 424/287,

424/289, 424/293, 424/295 Int. Cl. ..AOln 9/02, AOln 21/00 Field of Search ..424/245, 287, 289

M lMarch 13, 1973 [56] References Cited UNITED STATES PATENTS 2,799,615 7/1957 Heymons et al ..424/245 2,872,469 2/l959 Stevens ..424/289 X Primary Examiner-Albert T. Meyers Assistant Examiner-D. Moyer Attorney-Lane, Aitken, Dunner & Ziems [57] ABSTRACT The present invention relates to fungicidal compositions for agricultural and horticultural use comprising one or more kinds of metal salts of a-amino-yethylthio butyric acid such as copper a-amino-yethylthio butyrate, or manganese a-amino-y-ethylthio butyrate and one or more kinds of 8-oxyquinoline metal complex, such as copper or zinc 8-oxyquinolate along with adjuvants such as dispersing agent, emulsifier, or wetting agent. The composition of the present invention is remarkably effective when applied at low concentration for black spot of pear (Alernaria kikuchiana) or Helminthosporium leaf spot (Cochliobolus miyabeanus).

1 Claim, No Drawings FUNGICIDAL COMPOSITION COMPRISING COPPER 8-0XYQUINOLATE AND COPPER a- AMINO-'y-ETHYL-THIOBUTYRATE The present invention relates to fungicidal composi- 5 The names f compound, and he come"- tions for agricultural and horticultural use containing one or more kinds of metal salts of a-amino-yethylthiobutyric acid and one or more kinds of metal complex of 8-oxyquinoline, as the active ingredients.

Among the above given active ingredients, copper 8- oxyquinolate which is a typical metal complex of 8-oxyquinoline, is already used practically as a fungicide with almost no resulting phyto toxicity against plant life or almost no side effects upon exposure to human beings and cattle.

However, when compared with other fungicides, there is a drawback in that the fungicidal effect is inferior.

On the other hand, the other active ingredient, i.e., the metal salt of a-amino-y-ethylthiobutyric acid (hereinafter a-amino-y-ethylthio butyric acid referred to as ethionine) has the drawback that the fungicidal effect is inferior.

It has now been discovered that by combining a metal complex of 8-oxyquinoline with the metal salts of ethionine both of which had previously exhibited inferior fungicidal activities a mixture is produced which has outstanding fungicidal activity even when applied at lower concentrations.

The fungicidal compositions of the present invention is generally used for the control of pathogenic fungi, but it has remarkable effect against Alternaria kikuchiana (Black spot of pear) and Cochliobolus miyabeanus (Helminthosporium leaf spot of rice plant) and is not poisonous against human beings, cattle and plants.

As the metal complex of 8-oxyquinoline to be used in the present invention, the following are illustrative.

Melting point above 270C Name of compounds copper 8-oxyquinolate manganese S-oxyquinolate zinc 8-oxyquinolste cobalt 8-oxyquinolate nickel S-oxyquinolate iron B-oxyquinolate lead 8-oxyquinolate As the metal salts of ethionine the following are illustrative;

Melting point decomposed above 270C For a better understanding, the fungicidal effect of the mixtures of the present invention will be illustrated by the following experiments.

EXPERIMENT l SkORE GERMINATION TEST The spores of Alternaria kikuchiana (Black spot of pear) was mixed in Hopkins medium (PHS) containing the predetermined concentration of the fungicidal compositions, and the spore germinating ratio was observed after 18 hours incubation, and the result is given in Table 1.

TABLE 1 Spore germinating trations of active ingredients (meg/ml) ratio (51) Copper oxyquinolate Copper ethionine 2.5 0 80.8 1.5 1.0 20.5 1.25 1.25 22.7 1.0 1.5 50.3 0 2.5 86.6 Zinc oxyquinolate Zinc ethionine 25 0 70.4 15 10 65.9 12.5 12.5 0 10 15 64.8 0 25 94.9 Manganese oxyquinolate Manganese ethionine 25 0 80.5 15 10 30.3 12.5 12.5 30.0 10 15 50.4 0 25 96.5 Lead oxyquinolate Lead ethionine 50 0 70.0 30 20 30.0 25 25 28.5 20 30 60.0 0 50 90.5 Cobalt oxyguinolate Cobalt ethionine 50 0 77.3 30 20 31.2 25 25 30.8 20 30 78.5 0 50 93.6 Nickel oxyquinolate Nickel ethionine 50 0 89.8 30 20 31.6 25 25 33.2 20 30 76.5 0 50 9 l .8 Iron oxyquinolate lron ethionine 5O 0 96.5 30 20 43.5 25 25 31.5 20 30 78.9 0 50 96.7 Copper oxyquinolate Zinc ethionine 25 0 60.0 15 10 20.0 12.5 12.5 10.0 10 15 31.2 0 25 59.5 Zinc oxyquinolate Manganese ethionine 25 0 70.4 15 10 63 .0 12.5 12.5 21.5 l0 15 74.0 0 25 96.5 Manganese oxyquinolate Lead ethionine 25 0 80.5 15 10 65 .2 12.5 12.5 38.0 10 15 75.5 0 25 90.5 Lead oxyquinolate Cobalt ethionine 50 0 70.0 25 25 34.0 20 30 65 .0 0 50 93.6 Cobalt oxyquinolate Nickel ethionine 50 0 77.3 25 25 43.5 20 30 55.2 0 50 91.8 Nickel oxyqulnolate lron ethionine 50 0 89.8 25 25 45.0 20 30 65.0 0 50 96.7 Zinc oxyquinolate Copper ethionine 5.0 0 99.3 2.5 2.5 43.0 0 5.0 78.8 Manganese oxyquinolate Copper ethionine 5.0 0 96.8 2.5 2.5 51.3 0 5.0 78.8 Lead oxyquinolate Copper ethionine 0 5.0 78.8 Cobalt oxyquinolate Copper ethionine O 5.0 78.8 Nickel oxyquinolate Copper ethionine 0 5.0 78.8 Iron oxyquinolate Copper ethionine As is apparent from Table I, the mixture of the present invention, i.e., metal complex of 8-oxyquinoline and metal salts of ethionine inhibited remarkably spore-germination of Alternaria kikuchiana when compared with the case in which each component was used respectively.

EXPERIMENT 2 The preventive effect on the disease of black spot of pear (Alternaria kikuchiana) by means of leaf detached test The detached leaf of pear (Niju Seiki species) was dipped into the solution containing the predetermined concentration of the fungicidal compositions, and it was taken out and dried, and thereafter spores of Alternaria kikuchiana were inoculated by means of spraying, and the inoculated leaf was kept the moist chamber at 27C, and thereafter the degree of disease development was observed.

The obtained result is shown in Table 2 and Table 3.

The degree of the development of disease was classified into the following six grades.

Index of disease development Healthy 0 Diseased area I- 20% l 21- 40% 2 41- 60% 3 61- 80% 4 81- 100% 5 TABLE 2 Names of compounds and the concentrations of active ingredients (mcg/ml) Index of disease development Copper oxyquinolate Coppere thinonine 250 0 4.5 150 0 5.0 125 0 5.0 100 0 5.0 0 250 3.0 0 150 4- 0 125 5.0 0 100 5.0 150 100 L5 125 125 100 150 Manganese oxyquinolate Manganese ethionine 250 0 3.0 150 0 4.8 125 0 4.5 100 0 5.0 0 250 4.0 0 150 5.0 0 125 5.0 0 100 5.0 150 100 1.5 125 I25 2.0 100 I50 3.5 Zinc oxyquinolate Zinc ethionine Lead oxyquinolate Lead ethionine Cobalt oxyquinolate Cobalt ethionine Nickel oxyquinolate Nickel ethioninc Iron oxyquinolate Iron ethionine Difoltan N-tetrachloroethylthio-tetrahydrophthalimide TABLE 3 Names of compounds and the concen- Index of disease trations of active ingredients (meg/ml) development Manganese Cobalt Copper Oxyquinolate ethionine ethionine 250 0 0 4.5 150 0 0 5.0 125 0 0 5.0 0 0 5.0 0 250 0 4.0 0 150 O 5.0 0 0 5.0 0 100 0 5.0 0 0 250 3.0 0 0 I50 4.0 0 0 125 5.0 0 0 100 5.0 100 100 50 1.5 50 50 0.5 25 25 200 L0 EXPERIMENT 3 The preventive effect on the disease of Helminthosporium leaf sport of rice plant (Cochliobolus miyabeanus) l0 ml/pot of the solution containing the predetermined concentration of the fungicidal compositions was sprayed on 20 seedlings of rice plants at the stage of the three'leIVes in a pot, and after having dried the solution, the seedling were inoculated with spore suspension of Cochliobolus miyabeanus and kept in the moist chamber for overnight and thereafter kept in greenhouse, and 5 days after inoculation, the number of spots were counted.

The obtained results were shown in Table 4 and 5.

The preventive value in the table was calculated in accordance with the following equation;

Preventive value (7%) l-(number of spots per one leaf of treated plot/number of spots per leaf of untreated plot) X 100 TABLE 4 Names of compounds and the concen- Preventive trations of active ingredients (ppm) value (91:) Copper oxyquinolate Copper ethionine 200 40.5 150 50 87.9 100 100 92.8 50 150 81.7 0 200 43.2 Zinc oxyquinolate Zinc ethionine 500 0 48.2 250 250 89.4 0 500 55.3 Manganese oxyquinolate Manganese ethionine 500 63.4 250 250 88.2 0 500 64.3 Lead oxyquinolate Lead ethionine 500 0 62.1 250 250 70.0 0 500 32.7 Cobalt oxyquinolate Cobalt ethionine 500 0 41.8 250 250 48.6 0 500 35.5 Nickel oxyquinolate Nickel ethionine 500 0 42.2 250 250 50.9 0 500 30.4 Iron oxyquinolate lron ethionine TABLE Names of compounds and the concen- Preventive trations of active ingredients (ppm) value Copper Zinc Copper oxyquinolate ethionine ethionine 200 0 0 40.5 182 10 8 79.8 175 12 13 80.1 100 50 50 86.5 75 50 75 98.0 25 50 125 87.4 18 82 100 85.1 0 200 0 20.5 0 0 200 43.2

As is apparent from Table 4 and 5, the mixture of the present invention can effectively prevent Helminthosporium leaf spot of rice plant (Cochlibolus miyabeanus).

On the other hand, any phytotoxity against rice plant was not observed at all.

In the mixture of the present invention, the most appropriate blending ratio can be determined in accordance with the growing condition and stage of the particular plant, but the mixing ratio of 1 part of one or more kinds of metal complex of B-oxyquinoline and 0.1 to 10 parts of one or more kinds of metal salt of aamino-y-ethylthio butyric acid is the most preferable.

When the mixture of the present invention is practically used, it can be used in the form of powder, wettable powder, tablet or granule which is directly applied alone or by mixing along with carrier.

As the examples of carriers to be used in the present invention, clay, talc, diatomaceous earth, or bentonite or such like solid carriers can be given.

, The fungicidal compositions according to this invention may also include adjuv ants which are conyentlonally used in connection with agricultural chemicals such as a dispersing agent emulsifier wetting agent or binding agent.

The fungicidal compositions according to this invention in addition to the previously indicated active ingredients may also comprise a fungicide, insecticide, nematicide, herbicide, plant growth regulator, soil conditioner, fertilizer or such.

This invention is more concretely explained by the following examples.

Example 1 3 parts of manganese 8-oxyquinolate, 2 parts of manganese ethionine, and parts of clay or talc were sufficiently mixed and crushed to prepare powder which is directly sprayed.

Example 2 

